Porphyrin compositions

ABSTRACT

Novel metal porphyrin compositions useful as organic phosphors are provided. The novel compositions are prepared from commercially available porphyrin-containing starting materials. In one instance a novel palladium-containing porphyrin composition having a number average molecular weight of greater than 12,000 grams per mole was prepared from 5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)-21H-23H-porphyrin by reaction first with palladium(II) acetylacetonate, followed by reaction with 2-bromo-2-methylpropionyl bromide, and subsequent group transfer reaction of the alpha-bromo ester groups with 9,9-dioctyl-2-vinylfluorene in the presence of CuBr as a radical initiator. The product polymer exhibited a number average molecular weight of 12,884 grams per mole, a weight average molecular weight of 14,338 grams per mole, and a robust red phosphorescent emission. Porphyrin containing copoylmers comprising structural units derived from 9,9-dioctyl-2-vinylfluorene and 9-anthracenylmethyl methacrylate were prepared in a similar fashion.

This is a Non-Provisional of currently pending U.S. provisionalapplication No. 60/643,077, filed Jan. 11, 2005.

BACKGROUND

The invention relates to novel, metal-containing porphyrin heterocyclesand methods for their preparation.

Metal-containing porphyrin heterocycles represent an important anduseful class of organic compounds. Metal porphyrins are widelydistributed in nature and play, in certain instances, important roles invarious biological processes, such as photosynthesis. Syntheticmetal-containing porphyrins are well known and have been used in interalia studies of enzymatic catalysis and as useful catalysts in their ownright.

Certain metal-containing porphyrin heterocycles have been shown to beuseful as phosphorescent dopants in organic light-emitting devices.(See, for example, U.S. Pat. No.6,303,238).

Although much has been learned in earlier work, there is nonetheless aneed for new metal-containing porphyrin heterocycles which exhibit newor improved properties relative to known materials.

BRIEF DESCRIPTION

In one embodiment, the present invention provides a compositioncomprising a porphyrin heterocycle having structure I

wherein M is a divalent, trivalent or tetravalent metal ion; “a” is 0,1, 2, or a non-zero fraction having a value between 0 and 1; Y isindependently at each occurrence a charge balancing counterion; R¹ andR² are independently at each occurrence a halogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, a C₂-C₂₀ aromatic radical, orR¹ and R² may together form a divalent aliphatic radical, a divalentcycloaliphatic radical, or a divalent aromatic radical; R³ isindependently at each occurrence an organic radical having structure II

wherein Ar¹ is a C₂-C₅₀ aromatic radical; L¹ is a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;F is independently at each occurrence a structural unit derived from anolefin monomer selected from the group consisting of polycyclic olefinmonomers and heterocyclic olefin monomers;

-   “n” is independently at each occurrence an integer from 1 to about    200;-   Q is independently at each occurrence a hydrogen, a halogen, a    C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a    C₂-C₂₀ aromatic radical; and-   “m” is independently at each occurrence an integer from 1 to about    10.

In another embodiment, the present invention provides an organicphosphor comprising a porphyrin heterocycle having structure I.

In yet another embodiment, the present invention provides a method ofmaking a composition comprising a porphyrin heterocycle having structureI, the method comprising contacting in the presence of an initiatior aheterocyclic precursor compound having structure XVII

wherein M is a divalent, trivalent or tetravalent metal; “a” is 0, 1, 2,or a non-zero fraction having a value between 0 and 1; Y isindependently at each occurrence a charge balancing counterion; R¹ andR² are independently at each occurrence a halogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, a C₂-C₂₀ aromatic radical, orR¹ and R² may together form a divalent aliphatic radical, a divalentcycloaliphatic radical, or a divalent aromatic radical; R³ isindependently at each occurrence an organic radical having structureXVIII

wherein Ar¹ is a C₂-C₅₀ aromatic radical; L¹ is a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;Q is halogen susceptible to group transfer, a C₁-C₂₀ aliphatic radicalsusceptible to group transfer, a C₃-C₂₀ cycloaliphatic radicalsusceptible to group transfer, or a C₂-C₂₀ aromatic radical susceptibleto group transfer; and “m” is an integer from 1 to about 10;with at least one olefin monomer selected from the group consisting ofpolycyclic olefin monomers and heterocyclic olefin monomers.

DETAILED DESCRIPTION

Approximating language, as used herein throughout the specification andclaims, may be applied to modify any quantitative representation thatcould permissibly vary without resulting in a change in the basicfunction to which it is related. Accordingly, a value modified by a termor terms, such as “about” and “substantially”, are not to be limited tothe precise value specified. In at least some instances, theapproximating language may correspond to the precision of an instrumentfor measuring the value. Here and throughout the specification andclaims, range limitations may be combined and/or interchanged, suchranges are identified and include all the sub-ranges contained thereinunless context or language indicates otherwise.

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionand the examples included therein. In the following specification andthe claims which follow, reference will be made to a number of termswhich shall be defined to have the following meanings:

The singular forms “a”, “an” and “the” include plural referents unlessthe context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where the event occurs and instances where it does not.

As used herein, the term “organic” includes organometallic compounds.Thus, the phosphorescent metal-containing porphyrin compositionsprovided by the present invention fall within the scope of the term“organic phosphors”.

As used herein, the term “aromatic radical” refers to an array of atomshaving a valence of at least one comprising at least one aromatic group.The array of atoms having a valence of at least one comprising at leastone aromatic group may include heteroatoms such as nitrogen, sulfur,selenium, silicon and oxygen, or may be composed exclusively of carbonand hydrogen. As used herein, the term “aromatic radical” includes butis not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl,phenylene, and biphenyl radicals. As noted, the aromatic radicalcontains at least one aromatic group. The aromatic group is invariably acyclic structure having 4n+2 “delocalized” electrons where “n” is aninteger equal to 1 or greater, as illustrated by phenyl groups (n=1),thienyl groups (n=1), furanyl groups (n=1), naphthyl groups (n=2),azulenyl groups (n=2), anthraceneyl groups (n=3) and the like. Thearomatic radical may also include nonaromatic components. For example, abenzyl group is an aromatic radical which comprises a phenyl ring (thearomatic group) and a methylene group (the nonaromatic component).Similarly a tetrahydronaphthyl radical is an aromatic radical comprisingan aromatic group (C₆H₃) fused to a nonaromatic component —(CH₂)₄—. Forconvenience, the term “aromatic radical” is defined herein to encompassa wide range of functional groups such as alkyl groups, alkenyl groups,alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienylgroups, alcohol groups, ether groups, aldehyde groups, ketone groups,carboxylic acid groups, acyl groups (for example carboxylic acidderivatives such as esters and amides), amine groups, nitro groups, andthe like. For example, the 4-methylphenyl radical is a C₇ aromaticradical comprising a methyl group, the methyl group being a functionalgroup which is an alkyl group. Similarly, the 2-nitrophenyl group is aC₆ aromatic radical comprising a nitro group, the nitro group being afunctional group. Aromatic radicals include halogenated aromaticradicals such as 4-trifluoromethylphenyl,hexafluoroisopropylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CF₃)₂PhO—),4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl,3-trichloromethylphen-1-yl (i.e., 3-CCl₃Ph-),4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH₂CH₂CH₂Ph-), and the like.Further examples of aromatic radicals include 4-allyloxyphen-1-oxy,4-aminophen-1-yl (i.e., 4-H₂NPh-), 3-aminocarbonylphen-1-yl (i.e.,NH₂COPh-), 4-benzoylphen-1-yl, dicyanomethylidenebis(4-phen-1-yloxy)(i.e., —OPhC(CN)₂PhO—), 3-methylphen-1-yl, methylenebis(4-phen-1-yloxy)(i.e., —OPhCH₂PhO—), 2-ethylphen-1-yl, phenylethenyl,3-formyl-2-thienyl, 2-hexyl-5-furanyl,hexamethylene-1,6-bis(4-phen-1-yloxy) (i.e., —OPh(CH₂)₆PhO—),4-hydroxymethylphen-1-yl (i.e., 4-HOCH₂Ph-), 4-mercaptomethylphen-1-yl(i.e., 4-HSCH₂Ph-), 4-methylthiophen-1-yl (i.e., 4-CH₃SPh-),3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methylsalicyl), 2-nitromethylphen-1-yl (i.e., 2-NO₂CH₂Ph),3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphenl-1-yl,4-vinylphen-1-yl, vinylidenebis(phenyl), and the like. The term “aC₃-C₁₀ aromatic radical” includes aromatic radicals containing at leastthree but no more than 10 carbon atoms. The aromatic radical1-imidazolyl (C₃H₂N₂—) represents a C₃ aromatic radical. The benzylradical (C₇H₇—) represents a C₇ aromatic radical.

As used herein the term “cycloaliphatic radical” refers to a radicalhaving a valence of at least one, and comprising an array of atoms whichis cyclic but which is not aromatic. As defined herein a “cycloaliphaticradical” does not contain an aromatic group. A “cycloaliphatic radical”may comprise one or more noncyclic components. For example, acyclohexylmethyl group (C₆H₁₁CH₂—) is a cycloaliphatic radical whichcomprises a cyclohexyl ring (the array of atoms which is cyclic butwhich is not aromatic) and a methylene group (the noncyclic component).The cycloaliphatic radical may include heteroatoms such as nitrogen,sulfur, selenium, silicon and oxygen, or may be composed exclusively ofcarbon and hydrogen. For convenience, the term “cycloaliphatic radical”is defined herein to encompass a wide range of functional groups such asalkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups,conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups,ketone groups, carboxylic acid groups, acyl groups (for examplecarboxylic acid derivatives such as esters and amides), amine groups,nitro groups, and the like. For example, the 4-methylcyclopent-1-ylradical is a C₆ cycloaliphatic radical comprising a methyl group, themethyl group being a functional group which is an alkyl group.Similarly, the 2-nitrocyclobut-1-yl radical is a C₄ cycloaliphaticradical comprising a nitro group, the nitro group being a functionalgroup. A cycloaliphatic radical may comprise one or more halogen atomswhich may be the same or different. Halogen atoms include, for example;fluorine, chlorine, bromine, and iodine. Cycloaliphatic radicalscomprising one or more halogen atoms include2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl,2-chlorodifluoromethylcyclohex-1-yl,hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e.,—C₆H₁₀C(CF₃)₂C₆H₁₀—), 2-chloromethylcyclohex-1-yl,3-difluoromethylenecyclohex-1-yl, 4-trichloromethylcyclohex-1-yloxy,4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl,2-bromopropylcyclohex-1-yloxy (e.g., CH₃CHBrCH₂C₆H₁₀O—), and the like.Further examples of cycloaliphatic radicals include4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H₂NC₆H₁₀—),4-aminocarbonylcyclopent-1-yl (i.e., NH₂COC₅H₈—),4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy)(i.e., —OC₆H₁₀C(CN)₂C₆H₁₀O—), 3-methylcyclohex-1-yl,methylenebis(cyclohex-4-yloxy) (i.e., —OC₆H₁₀CH₂C₆H₁₀O—),1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl,2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy)(i.e., —OC₆H₁₀(CH₂)₆C₆H₁₀O—), 4-hydroxymethylcyclohex-1-yl (i.e.,4-HOCH₂C₆H₁₀O—), 4-mercaptomethylcyclohex-1-yl (i.e., 4-HSCH₂C₆H₁₀O—),4-methylthiocyclohex-1-yl (i.e., 4-CH₃SC₆H₁₀—), 4-methoxycyclohex-1-yl,2-methoxycarbonylcyclohex-1-yloxy (2-CH₃OCOC₆H₁₀O—),4-nitromethylcyclohex-1-yl (i.e., NO₂CH₂C₆H₁₀—),3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethylsilylcyclopent-1-yl,4-trimethoxysilylethylcyclohex-1-yl (e.g., (CH₃O)₃SiCH₂CH₂C₆H₁₀—),4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like. Theterm “a C₃-C₁₀ cycloaliphatic radical” includes cycloaliphatic radicalscontaining at least three but no more than 10 carbon atoms. Thecycloaliphatic radical 2-tetrahydrofuranyl (C₄H₇O—) represents a C₄cycloaliphatic radical. The cyclohexylmethyl radical (C₆H₁₁CH₂—)represents a C₇ cycloaliphatic radical.

As used herein the term “aliphatic radical” refers to an organic radicalhaving a valence of at least one consisting of a linear or branchedarray of atoms which is not cyclic. Aliphatic radicals are defined tocomprise at least one carbon atom. The array of atoms comprising thealiphatic radical may include heteroatoms such as nitrogen, sulfur,silicon, selenium and oxygen or may be composed exclusively of carbonand hydrogen. For convenience, the term “aliphatic radical” is definedherein to encompass, as part of the “linear or branched array of atomswhich is not cyclic” a wide range of functional groups such as alkylgroups, alkenyl groups, alkynyl groups, haloalkyl groups , conjugateddienyl groups, alcohol groups, ether groups, aldehyde groups, ketonegroups, carboxylic acid groups, acyl groups (for example carboxylic acidderivatives such as esters and amides), amine groups, nitro groups, andthe like. For example, the 4-methylpent-1-yl radical is a C₆ aliphaticradical comprising a methyl group, the methyl group being a functionalgroup which is an alkyl group. Similarly, the 4-nitrobut-1-yl group is aC₄ aliphatic radical comprising a nitro group, the nitro group being afunctional group. An aliphatic radical may be a haloalkyl group whichcomprises one or more halogen atoms which may be the same or different.Halogen atoms include, for example; fluorine, chlorine, bromine, andiodine. Aliphatic radicals comprising one or more halogen atoms includethe alkyl halides trifluoromethyl, bromodifluoromethyl,chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl,difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl,2-bromotrimethylene (e.g., —CH₂CHBrCH₂—), and the like. Further examplesof aliphatic radicals include allyl, aminocarbonyl (i.e., —CONH₂),carbonyl, 2,2-dicyanoisopropylidene (i.e., —CH₂C(CN)₂CH₂—), methyl(i.e., —CH₃), methylene (i.e., —CH₂—), ethyl, ethylene, formyl (i.e.,—CHO), hexyl, hexamethylene, hydroxymethyl (i.e., —CH₂OH),mercaptomethyl (i.e., —CH₂SH), methylthio (i.e., —SCH₃),methylthiomethyl (i.e., —CH₂SCH₃), methoxy, methoxycarbonyl (i.e.,CH₃OCO—), nitromethyl (i.e., —CH₂NO₂), thiocarbonyl, trimethylsilyl(i.e., (CH₃)₃Si—), t-butyldimethylsilyl, 3-trimethyoxysilypropyl (i.e.,(CH₃O)₃SiCH₂CH₂CH₂—), vinyl, vinylidene, and the like. By way of furtherexample, a C₁-C₁₀ aliphatic radical contains at least one but no morethan 10 carbon atoms. A methyl group (i.e., CH₃—) is an example of a C₁aliphatic radical. A decyl group (i.e., CH₃(CH₂)₉—) is an example of aC₁₀ aliphatic radical.

As noted, in one aspect the present invention provides a compositioncomprising porphyrin heterocycle I. In structure I, the metal M may beany metal ion which can insert into the interior cavity of theporphyrin. In one embodiment, M is a divalent metal ion, for examplePd²⁺ or Pt²⁺. In another embodiment, M is a trivalent metal ion, forexample Fe³⁺ or Co³⁺. In yet another embodiment, M is a tetravalentmetal ion, for example Ti⁺⁴. Those skilled in the art will appreciatethat when M is a metal ion having a charge greater than +2, one or morecharge balancing counterions Y will be present to preserve a net chargeof zero for the system. The charge balancing counterion Y may be anyanion. Those skilled in the art will understand that when the chargebalancing counterion is a polyvalent anion such as the dianion ofmalonic acid, the anion may associate with one or more metal ionsdepending on the charge of the metal ion. This point is illustrated byway of the following examples. When M is Fe³⁺ and Y is acetate (CH₃CO₂⁻) the charge on the metal will be balanced by a single acetate anionfor each molecule having structure I and the value of “a” will be 1.Alternatively, suppose M is Fe³⁺ and Y is the dianion of malonic acid(⁻O₂CCH₂CO₂ ⁻), only a single additional negative charge is needed tobalance the overall charge of the heterocycle I and thus the value of“a” will be a fraction (½). In such a case, the polyvalent anion(malonate) will be associated with two molecules of the porphyrinheterocycle. In certain embodiments, the value of “a” will be zero, 1 or2. As noted with the example just cited, however, fractional values of“a” between 0 and 1 are also possible. Thus, “a” is defined as 0, 1, 2,or a non-zero fraction having a value between 0 and 1.

The groups R¹ and R² are, as noted, independently at each occurrence ahalogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, aC₂-C₂₀ aromatic radical, or R¹ and R² may together form a divalentaliphatic radical, a divalent cycloaliphatic radical, or a divalentaromatic radical. Structures Ia-Ie in Table 1 illustrate variousembodiments of the present invention wherein the groups R¹ and R² arevaried. For the purpose of fully illustrating of these non-limitingexamples, in structures Ia-Ie; M is Pd²⁺, “a” is zero, and R³ (discussedin detail hereinafter) is the group —Ar¹(L¹(F)_(n)Q)_(m) wherein Ar¹ hasstructure XII (discussed in detail hereinafter), L¹ has structure XIII(discussed in detail hereinafter), F is a moiety derived from9,9-dioctyl-2-vinylfluorene, “n” is 5, Q is Br, and “m” is 2. Thus, eachof the examples Ia-Ie represents a single and unique species of thepresent invention. Those skilled in the art will understand that theembodiment Ic represents a case in which R¹ and R² together form adivalent aliphatic radical (—(CH₂)₆—). Similarly, those skilled in theart will understand that the embodiments Id and Ie represent cases inwhich R¹ and R² together form a divalent aromatic radical (—(CH₂)₃CHPh-)and a divalent cycloaliphatic radical (—(CH₂)₃CHcyclohexyl-)respectively.

TABLE 1 ILLUSTATIVE VARIATIONS IN R¹ AND R² Entry Structure R¹ StructureR² Ia Et Et Ib H Et Ic

Id

Ie

As noted, R³ is independently at each occurrence an organic radicalhaving structure II

wherein wherein Ar¹ is a C₂-C₅₀ aromatic radical; L¹ is a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical; F is independently at each occurrence a structural unit derivedfrom an olefin monomer selected from the group consisting of polycyclicolefin monomers and heterocyclic olefin monomers;

-   “n” is independently at each occurrence an integer from 1 to about    200;-   Q is independently at each occurrence a hydrogen, a halogen, a    C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a    C₂-C₂₀ aromatic radical; and-   “m” is independently at each occurrence an integer from 1 to about    10.

The group Ar¹ is an aromatic radical which is at least divalent, thegroup Ar¹ being attached to both the porphyrin core and the pendantgroup(s) (L¹(F)_(n)Q). In one embodiment, the group R³ is elaboratedfrom the reaction of a porphyrin ring system bearing reactive pendantgroups. For example, the condensation of pyrrole with4-hydroxybenzaldehyde affords after treatment with a source of palladiumions (e.g. palladium acetylacetonate) a metal-containing heterocyclehaving structure I wherein M is Pd²⁺, “a” is 0, R¹ and R² are hydrogen,and R³ is the 4-hydroxyphenyl radical. Thus, the Ar¹ group present invarious embodiments of the present invention may be derived from anysuitably functionalized aromatic aldehyde, for example4-hydroxybenzaldehyde, 4-carboxybenzaldehyde, 3,5-dihydroxybenzaldehyde,3,5-carboxybenzaldehyde, and the like. The other moieties present in R³in various embodiments of the invention, L¹, F, and Q may be attachedvia the functional group of the suitably functionalized aromaticaldehyde as discussed hereinafter.

In one embodiment, the group Ar¹ present in structure II is a divalentaromatic radical having structure XI

In an alternate embodiment, the group Ar¹ present in structure II is atrivalent aromatic radical having structure XII.

It should be noted (with continued reference to structure II), that whenAr¹ is a trivalent aromatic radical having structure XII, the group Ar¹bears two pendant groups (L¹(F)_(n)Q) and “m” has a value of 2.

The group L¹ is independently at each occurrence a divalent C₁-C₂₀aliphatic radical, a divalent C₃-C₂₀ cycloaliphatic radical, or adivalent C₂-C₂₀ aromatic radical. In one embodiment, L¹ is a divalentaliphatic radical having structure XIII.

The group F is independently at each occurrence a structural unitderived from an olefin monomer selected from the group consisting ofpolycyclic olefin monomers and heterocyclic olefin monomers. Polycyclicolefin monomers are olefin monomers comprising at least two ringstructures and are illustrated by polycyclic olefin monomers III, IV, V,and VI

wherein R⁴ and R⁵ are independently hydrogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;L is a bond, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphaticradical, or a C₂-C₂₀ aromatic radical; and R⁶ is hydrogen, halogen, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical.

Olefin monomers III are illustrated by 9,9-dioctyl-2-vinylfluorene;9,9-dinonyl-2-vinylfluorene; 9,9-heptyl-2-vinylfluorene;9,9-dimethyl-2-vinylfluorene; 9,9-dioctyl-3-vinylfluorene;9,9-dioctyl-4-vinylfluorene; 9,9-dioctyl-2-acryloylfluorene;9,9-dioctyl-2-methacryloylfluorene;9,9-dioctyl-2-(1-trifluoromethylvin-1-yl)fluorene;9,9-dioctyl-2-(1-fluorovin-1-yl)fluorene;9,9-dioctyl-2-(1-chorovin-1-yl)fluorene; and the like.

Olefin monomers IV are illustrated by 9-vinylanthracene,9-acryloylanthracene; 9-methacryloylanthracene;9-anthracenylmethylmethacrylate (See Example 8 herein); and the like.

Olefin monomers V are illustrated by 1-vinylanthracene,1-acryloylanthracene; 1-methacryloylanthracene;1-anthracenylmethylmethacrylate; 2-vinylanthracene,2-acryloylanthracene; 2-methacryloylanthracene;2-anthracenylmethylmethacrylate (See Example 8 herein); and the like.

Olefin monomers VI are illustrated by 1-vinylnaphthalene;1-acryloylnathalene; 1-methacryloylnathalene; 1-acryloyloxynathalene;1-methacryloyloxynathalene; 2-vinylnaphthalene; 2-acryloylnathalene;2-methacryloylnathalene; 2-acryloyloxynathalene;2-methacryloyloxynathalene; 2-(1-trifluoromethylvin-1-yl)naphthalene;2-(1-fluorovin-1-yl)naphthalene; and the like.

Heterocyclic olefin monomers are olefin monomers comprising at least oneheterocyclic ring structure and are illustrated by heterocyclic olefinmonomers VII, VIII, IX, and X

wherein T is —O—, —S—, —Se—, —SS—, —SeSe—,—SO—, —SO₂—, —NH—, —NHNH—, adivalent C₁-C₂₀ aliphatic radical comprising at least one heteroatom, adivalent C₃-C₂₀ cycloaliphatic radical comprising at least oneheteroatom, or a divalent C₂-C₂₀ aromatic radical comprising at leastone heteroatom; R⁴ and R⁵ are independently at each occurrence hydrogen,a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical; “b” is independently at each occurrence 0, 1, 2, 3, or4; “c” is a number from 0 to about 10; L² is a bond, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;and R⁶ is hydrogen, halogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical.

Heterocyclic olefin monomers VII are illustrated by 1-vinyldibenzofuran(T is oxygen); 1-vinyldibenzothiophene (T is sulfur);1-vinyldibenzoselenophene (T is selenium); 2-vinyldibenzofuran;2-vinyldibenzothiophene; 2-vinyldibenzoselenophene; 3-vinyldibenzofuran;3-vinyldibenzothiophene; 3-vinyldibenzoselenophene; 4-vinyldibenzofuran;4-vinyldibenzothiophene; 4-vinyldibenzoselenophene;2-acryloyldibenzofuran; 2-acryloyldibenzothiophene;2-acryloyldibenzoselenophene; 2-methacryloyldibenzofuran;2-methacryloyldibenzothiophene; 2-methacryloyldibenzoselenophene;3-vinyl-2,8-dioctyldibenzofuran; 4-vinyl-2,8-dimethyldibenzofuran;3-vinyl-2,8-dioctyldibenzothiophene;2-vinyl-2,8-dioctyldibenzoselenophene; and the like.

Heterocyclic olefin monomers VIII are illustrated by N-vinylcarbazole,N-allyl carbazole, N-(1-buten-4-yl)carbazole, N-acryloylcarbazole,N-methacryloylcarbazole; and the like.

Heterocyclic olefin monomers IX are illustrated by 2-vinylthiophene(“c”=0); 3,4-dimethyl-2-vinylthiophene; 5-vinyl-2,2′-dithiophene;2-vinyl-3,4-dimethylthiophene trimer (See Example 20 herein);2-vinyl-3,4-dimethylthiophene dimer;2-vinyl-3-methyl-4-cyclohexylthiophene dimer (See Example 26 herein);and the like.

Heterocyclic olefin monomers X are illustrated by are illustrated by2-vinylselenophene (“c”=0); 3,4-dimethyl-2-vinylselenophene;5-vinyl-2,2′-diselenophene; 2-vinyl-3,4-dimethylselenophene trimer;2-vinyl-3,4-dimethylselenophene dimer;2-vinyl-3-methyl-4-cyclohexylselenophene dimer; and the like.

As noted, in one embodiment, “n” in structure II is independently ateach occurrence an integer from 1 to about 200. As a result,heterocyclic compound I may be of relatively low molecular weight whenthe value of “n” is about 1, but because the R³ group is repeated 4times within structure I, the molecular weight of the heterocycliccompound I increases rapidly with an increasing value of “n”. In oneembodiment, each R³ group is characterized a distinct and differentvalue of “n”. It is convenient moreover, to regard compositions havingstructure I as being characterized by an average value of “n”, theaverage value of “n” being (when “m” is 1) the sum of the values of “n”for each of the four R³ groups divided by 4. It will be appreciated bythose skilled in the art that other methods of determining the averagevalue of “n” are also available. For example, in the case of Example 7herein, the average value of “n” was found to be about 3.2 bydetermining the number average molecular weight of compound I by gelpermeation chromatography, determining (by difference) what portion ofthe number average molecular weight in grams per mole was attributableto structural units derived from 9,9-dioctyl-2-vinylfluorene, dividingthat value by the molecular weight of 9,9-dioctyl-2-vinylfluorene, todetermine the total number of structural units derived from9,9-dioctyl-2-vinylfluorene, and dividing that value by eight. There isno requirement that the average value of “n” be an integer. For example,in one embodiment, the average value of “n” is a non-integer value suchas 3.2 (See Example 7 herein).

In one embodiment, “n” independently at each occurrence has a value in arange from about 1 to about 50. In an alternate embodiment, “n”independently at each occurrence has a value in a in a range from about1 to about 25. In yet another embodiment, “n” independently at eachoccurrence has a value in a in a range from about 1 to about 10.

The group Q is independently at each occurrence a hydrogen, a halogen, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical. In one embodiment, the group Q represents a moietywhich is susceptible to “group transfer” reaction. That is, Q in thepresence of an initiator may participate in a group transfer reaction orgroup transfer polymerization. Examples 7 and 8 of the instantapplication are illustrative of group transfer reactions in which thegroup transferred, Q, is a bromine atom (atom transfer) In the Examples7 and 8 just referred to, an initiator, cuprous bromide (CuBr), isemployed in order to effect the group transfer polymerization. Thus, inone embodiment of the present invention, Q is a bromine atom. Grouptransfer reactions involving the transfer of a single atom are sometimesreferred to as “atom transfer” reactions. In an alternate embodiment, Qis an organic moiety susceptible to group transfer reaction. Thus, inone embodiment, Q is a moiety having structure XVI. The foregoingdiscussion should not be read, however, to limit Q to groups susceptibleto participation in a group transfer reaction or group transferpolymerization.

As noted, “m” is independently at each occurrence an integer from 1 toabout 10. In one embodiment, the value of “m” is determined by thenumber and reactivity of functional groups present in an aromaticaldehyde used in the preparation of the porphyrin precursor. Thus, forexample, condensation of pyrrole with 3,5-dihydroxybenzaldehyde affordsa porphyrin precursor having 8 reactive hydroxyl groups which may beused to elaborate the compositions of the present invention. Under suchcircumstances, the moiety Ar¹ will have structure XII and “m” will havea value of 2. Those skilled in the art will understand that the highervalues of “m” are achievable. In one embodiment, a heterocyclicprecursor porphyrin having 12 reactive hydroxyl groups which may be usedto elaborate the compositions of the present invention, is prepared byreacting an aromatic aldehyde having three hydroxy groups with pyrrole.Synthetic methods for the preparation of such precursor porphyrins arewell known in the art. See for example, The Porphyrin Handbook, KarlKadish, Kevin Smith and Roger Guilard Ed.s (Academic Press, 1999).

In one embodiment, the present invention provides a compositioncomprising heterocyclic structure I, wherein “a” is 0; M is selectedfrom the group consisiting of Pd²⁺ and Pt²⁺; R¹ and R² are H; Ar¹ is anaromatic radical selected from the group consisting of divalent aromaticradicals XI and XII;

L¹ is a divalent aliphatic radical having structure XIII;

F is an olefin monomer-derived moiety having structure XIV

wherein R⁴ and R⁵ are independently at each occurrence hydrogen, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical, and R⁶ is independently at each occurrence a halogen,a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical;

“n” is independently at each occurrence an integer from 2 to about 10; Qis Br; and “m” is 1 or 2.

In an alternate embodiment, the present invention provides a compositioncomprising heterocyclic structure I, wherein “a” is 0; M is selectedfrom the group consisiting of Pd²⁺ and Pt²⁺; R¹ and R² are H; Ar¹ is anaromatic radical selected from the group consisting of divalent aromaticradicals XI and XII;

L¹ is a divalent aliphatic radical having structure XIII;

F is an olefin monomer-derived moiety having structure XV

wherein R⁴ is independently at each occurrence hydrogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical, and R⁶ is independently at each occurrence a halogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical;

“b” is independently at each occurrence 0, 1, or 2; “c” is a number from0 to about 10; “n” is independently at each occurrence an integer from 2to about 10; Q is Br; and “m” is 1 or 2.

The compositions of the present invention include compositions having,in one embodiment, a number average molecular weight in a range fromabout 1000 grams per mole to about 500,000 grams per mole. In analternate embodiment, the composition of the present invention has anumber average molecular weight in a range from about 1000 grams permole to about 25,000 grams per mole. In yet another embodiment, thecomposition of the present invention has a number average molecularweight in a range from about 2000 grams per mole to about 10,000 gramsper mole. Number average molecular weights may be determined by avariety of methods, for example by proton NMR or gel permeationchromatography. The molecular weight ranges given here are determined bygel permeation chromatography.

In one embodiment, the present invention provides an organic phosphorcomprising heterocyclic structure I. In an alternate embodiment, thepresent invention provides an organic phosphor comprising heterocyclicstructure I, said organic phosphor exhibiting a red phosphorescence whenirradiated.

In one embodiment, the present invention provides an organic phosphorhaving structure I wherein “a” is 0, and M is selected from the groupconsisting of Pd²⁺ and Pt²⁺. In an alternate embodiment, the presentinvention provides an organic phosphor having structure I wherein “a” is0, and M is Pt²⁺. In yet another embodiment, the present inventionprovides an organic phosphor having structure I wherein “a” is 0, and Mis Pd²⁺.

In yet another aspect, the present invention provides a method for thepreparation of a composition comprising heterocyclic structure I. Themethod comprises contacting in the presence of an initiatior aheterocyclic precursor compound having structure XVII

wherein M is a divalent, trivalent or tetravalent metal; “a” is 0, 1, 2,or a non-zero fraction having a value between 0 and 1; Y isindependently at each occurrence a charge balancing counterion; R¹ andR² are independently at each occurrence a halogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, a C₂-C₂₀ aromatic radical, orR¹ and R² may together form a divalent aliphatic radical, a divalentcycloaliphatic radical, or a divalent aromatic radical; R³ isindependently at each occurrence an organic radical having structureXVIII

wherein Ar¹ is a C₂-C₅₀ aromatic radical; L¹ is a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;Q is a halogen susceptible to group transfer, a C₁-C₂₀ aliphatic radicalsusceptible to group transfer, a C₃-C₂₀ cycloaliphatic radicalsusceptible to group transfer, or a C₂-C₂₀ aromatic radical susceptibleto group transfer; and “m” is an integer from 1 to about 10;with at least one olefin monomer selected from the group consisting ofpolycyclic olefin monomers and heterocyclic olefin monomers.

As used herein, the term “susceptible to group transfer” means that themoiety being described can be induced to participate in a group transferreaction or group transfer polymerization. For the purposes of thisdisclosure, the terms “group transfer reaction” and “group transferpolymerization” are defined to include “atom transfer reaction” and“atom transfer polymerization”. For example, the reaction described inExample 7 of the instant invention represents a group transfer reactionin which the “group” transferred is a bromine atom.

EXAMPLES

The following examples are intended only to illustrate methods andembodiments in accordance with the invention, and as such should not beconstrued as imposing limitations upon the claims.

Preparation of Porphyrin Intermediates

Example 1

Preparation of 5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)porphyrinpalladium(II) XIX: A 50 mL serum vial containing 30 mL of benzonitrilewas charged with palladium(II) acetylacetonate (0.475 g, 1.56 mmoles,Strem Chemicals, Newburyport, Mass., USA) and5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)-21H-23H-porphyrin (1.0 g,1.3 mmoles, TCI Chemicals, Tokyo, Japan). The solution was sealed with acrimp cap and degassed under bubbling nitrogen for 30 minutes. Thedegassed solution was then heated to 190° C. in an aluminum block withstirring for 23 hours. The solution was allowed to cool to ambienttemperature before slow precipitation into 100 mL chloroform to affordpalladium complex XIX (wherein, making reference to structure I: M=Pd²⁺,“a”=0, R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m) wherein “m” is 0 and Ar¹ is3,5-dihydroxyphenyl) as a bright red precipitate which was collected byvacuum filtration and dried in vacuo (65° C., 18 hours, 1.1 g, 1.29mmoles, 99%). ¹H-NMR (d₆-DMSO) δ 6.64 (4H, t), 6.98 (8H, d), 8.89 (8H,s).

Example 2

Preparation of heterocyclic precursor compound XX,5,10,15,20-tetrakis(3′,5′-bis(2-bromo-2-methylpropionyloxy)phenyl)porphyrinpalladium(II): To a solution of5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)porphyrin palladium(II) XIX(1.1 g, 1.29 mmoles) in pyridine (20 mL) was added α-bromoisobutyrylbromide (5.0 g, 21.7 mmoles, Aldrich, Milwaukee, Wis., USA). After theinitial exotherm, pyridinium hydrobromide precipitated. Once the deepred mixture was cooled to ambient temperature, 10 mL of distilled waterwas added to quench unreacted α-bromoisobutyryl bromide. The mixture wasfiltered to remove the pyrdinium hydrobromide salt. Pyridine was removedby rotary evaporation leaving a dark red oil. The dark red oil wasdissolved in a minimum amount of methylene chloride and precipitatedinto methanol to afford the product octaester XX (wherein, makingreference to structure I: M=Pd²⁺, “a”=0, R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m)wherein Ar¹ has structure XII, L¹ has structure XIII, Q is Br, “n” is 0,and “m” is 2) as a dark red solid (2.19 g, 1.07 mmoles, 83%). ¹³C-NMR(CDCl₃) δ 30.62, 55.03, 114.39, 119.63, 124.77, 131.55, 141.39, 143.47,149.52, 170.03.

Example 3

Preparation of 5,10,15,20-tetrakis(4′-hydroxyphenyl)porphyrinpalladium(II) XXI: To 15 mL of stirred benzonitrile in a 20 mL serumvial was charged palladium(II) acetylacetonate (0.370 g, 1.21 mmoles,Strem Chemicals, Newburyport, Mass., USA) and5,10,15,20-tetrakis(4′-hydroxyphenyl)-21H-23H-porphyrin (0.75 g, 1.1mmoles, Aldrich Chemical, Milwaukee, Wis., USA). The vial was sealedwith a crimp cap and degassed with nitrogen for 30 minutes. The degassedsolution was then stirred and heated at 190° C. in an aluminum block for23 hours. The solution containing the product was allowed to cool toambient temperature before slow precipitation into 50 mL chloroform. Thebright red precipitate was collected by vacuum filtration and dried invacuo (65° C., 10 hours) to give the product XXI (wherein, makingreference to structure I: M=Pd²⁺, “a”=0, R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m)wherein “m” is 0 and Ar¹ is 4-hydroxyphenyl) (0.78 g, 1.0 mmoles, 99%).¹H-NMR (d₆-DMSO) δ 7.20 (8H, d), 7.95 (8H, d), 8.85 (8H, s), 9.96 (4H,s).

Example 4

Preparation of heterocyclic precursor compound XXII,5,10,15,20-tetrakis(4′-(2-bromo-2-methylpropionyloxy)phenyl)porphyrinpalladium(II): To a solution of5,10,15,20-tetrakis(3′,5′-di(hydroxy)phenyl)porphyrin palladium(II)(0.35 g, 0.44 mmoles) in pyridine (5 mL) was added 2-bromoisobutyrylbromide (0.93 g, 4.0 mmoles). After the initial exotherm, pyridiniumhydrobromide was observed to precipitate. The deep red mixture wascooled to ambient temperature, and 2 mL of distilled water was added toquench unreacted 2-bromoisobutyryl bromide. The resultant mixture wasfiltered and the filtrate was concentrated by rotary evaporation to givea dark red oil. The dark red oil was dissolved in a minimum amount ofmethylene chloride and precipitated into methanol to afford uponfiltration the product tetraester XXII (wherein, making reference tostructure I: M=Pd²⁺, “a”=0, R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m) wherein Ar¹has structure XI, L¹ has structure XIII, Q is Br, “n” is 0, and “m”is 1) as a dark red solid (2.19 g, 1.07 mmoles, 83%). ¹H-NMR (CDCl₃) δ2.26 (24H, s), 7.59 (8H, d), 8.23 (8H, d), 8.87 (8H, s).

Example 5

Preparation of palladium heterocycle XXIII: To 5 mL of stirredbenzonitrile in a 20 mL serum vial was charged palladium(II)acetylacetonate (15 mg, 0.05 mmoles, Strem Chemicals, Newburyport,Mass., USA) and5,10,15,20-tetrakis(3′,5′-bis(2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1-piperidinyloxy)ethoxycarbonyl)phenyl)porphyrin(100 mg, 0.03 mmoles, Frontier Scientific, Logan, Utah, USA). The vialwas sealed with a crimp cap and degassed with nitrogen for 15 minutes.The degassed solution was then stirred and heated at 150° C. in analuminum block with stirring for 15 hours. The solution was allowed tocool to ambient temperature before slow precipitation into 50 mLhexanes. The collected dark orange solid was redissolved in 1 mL THF andre-precipitated in hexanes to afford a bright orange precipitate whichwas collected by vacuum filtration and dried in vacuo (65° C., 18 hours)to afford the product palladium heterocycle5,10,15,20-tetrakis(3′,5′-bis(2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1-piperidinyloxy)ethoxycarbonyl)phenyl)porphyrinpalladium (II) XXIII (wherein, making reference to structure I: M=Pd²⁺,“a”=0, R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m) wherein Ar¹ is the trivalentaromatic radical 3,5-dicarbonyl-phen-1-yl, L¹ is the divalent aromaticradical —OCH₂CH(Ph)-, Q is a C₉ cycloaliphatic radical having structureXVI, “n” is 0, and “m” is 2) ((49 mg, 0.015 mmoles, 47%). ¹H-NMR (CDCl₃)δ 8.81 (8H, s), 8.30 (12H, m), 7.52 (40H, br m), 5.25 (8H, m, ABX), 5.05(8H, m, ABX), 4.79 (8H, m, ABX, 1.75-1.18 (96H, m), 1.15 (24H, s) 0.85(24H, s).

Example 6

Preparation of palladium heterocycle XXIV: A 20 mL serum vial containing5 mL of benzonitrile was charged with palladium(II) acetylacetonate (39mg, 0.05 mmoles) and5,10,15,20-tetrakis(4′-(2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1-piperidinyloxy)ethoxycarbonyl)phenyl)porphyrin(200 mg, 0.11 mmoles, Frontier Scientific, Logan, Utah, USA). The vialwas sealed with a crimp cap and degassed with nitrogen for 15 minutes.The degassed solution was then stirred and heated at 150° C. in analuminum block for 15 hours. The solution was allowed to cool to ambienttemperature before slow precipitation into 50 mL of hexanes. Thecollected dark orange solid was then redissolved in 1 mL THF andre-precipitated in hexanes to afford a bright orange precipitate whichwas collected by vacuum filtration and dried in vacuo (65° C., 18hours). The product palladium heterocycle XXIV (196 mg, 1.29 mmoles,93%)5,10,15,20-tetrakis(4′-(2-phenyl-2-(2′,2′,6′,6′-tetramethyl-1-piperidinyloxy)ethoxycarbonyl)phenyl)porphyrinpalladium (II) (wherein, making reference to structure I: M=Pd, “a”=0,R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m) wherein Ar¹ is the divalent aromaticradical 4-carbonyl-phen-1-yl, L¹ is the divalent aromatic radical—OCH₂CH(Ph)-, Q is a C₉ cycloaliphatic radical having structure XVI, “n”is 0, and “m” is 1) was characterized by proton NMR. ¹H-NMR (CDCl₃) δ8.85 (8H, s), 8.30 (16H, d), 7.48 (20H, m), 5.22 (4H, t, ABX), 5.00 (4H,dd, ABX), 4.77 (4H, dd, ABX), 1.72-1.20 (48H, m), 1.15 (12H, s) 0.85(12H, s).

The structures of intermediates XIX-XXIV discussed in Examples 1-6 aregathered in Table 2.

TABLE 2 INTERMEDIATES R³ Entry* Ar¹ L¹ F Q n m XIX

— — — — 0 XX

— Br 0 2 XXI

— — — — 0 XXII

— Br 0 1 XXIII

—

0 2 XXIV

—

0 1 *Structures are referenced to heterocycle I wherein M = Pd²⁺, “a” =0, R¹ = R² = H, and R³ = Ar¹(L¹(F)_(n)Q)_(m)Group/Atom Transfer Polymerization

Example 7

Polymer XXV: A 20 mL serum vial containing 5 mL solution of anisole wascharged with the heterocyclic precursor compound XX (25 mg, 0.05 mmoles)prepared in Example 2, 2-vinyl-9,9-dioctylfluorene (1.01 g, mmoles, SeeExample 12 below), copper(I) bromide (28 mg, mmoles), andpentamethylenediethyltriamine (33.7 mg). The vial was sealed with acrimp cap and degassed with nitrogen for 15 minutes. The degassedsolution was then stirred and heated at 90° C. in an aluminum block for1 hour whereupon the viscosity of the reaction solution was observed tobe appreciably higher as evidenced by persistence of bubbles at theupper meniscus of the solution. The solution was allowed to cool toambient temperature before slow precipitation into 40 mL methanol. Apink fluffy solid was collected by vacuum filtration and redissolved in1 mL methylene chloride and re-precipitated in methanol to afford afluffy light solid which was collected by vacuum filtration and dried invacuo (65° C., 4 hours) to afford the product polymer (156 mg) havingstructure XXV (wherein, making reference to structure I: M=Pd²⁺, “a”=0,R¹=R²=H, R³=Ar¹(L¹(F)_(n)Q)_(m) wherein Ar¹ has structure XII, L¹ hasstructure XIII, Q is Br, “n” has an average value of about 3.2, and “m”is 2). The molecular weight of the product polymer was determined by gelpermeation chromatography (GPC) and molecular weights are referenced topolystyrene (PS) molecular weight standards. M_(w)=14338 grams per mole,Mn=12884 grams per mole. The average value of “n” was determined to beabout 3.2 based upon the number average molecular weight (12884 gramsper mole). The UV-Vis (chloroform) spectrum exhibited absorption maximaat 275, 296, 308, 417, 523, 599 nanomers. Solid state excitation of theproduct polymer with a UV lamp revealed a robust, red phosporesentemission.

Example 8

Polymer XXVI: To a 20 mL serum vial containing 4 mL dry toluene wascharged palladium porphyrin prepared in Example 2 (50 mg, 0.1 mmoles),2-vinyl-9,9-dioctylfluorene (0.4 g, 0.96mmoles, See Example 12 below),and 9-anthracenylmethyl methacrylate (0.312 grams 1.1 mmoles), copper(I)bromide (54 mg), and pentamethylenediethyltriamine (70 mg, mmoles). Thevial was sealed with a crimp cap and degassed with nitrogen for 15minutes. The degassed solution was then stirred and heated at 90° C. inan aluminum block for 30 minutes after which time the product mixturehad a honey-like viscosiy. The viscous product solution was allowed tocool to ambient temperature before slow precipitation into 40 mLmethanol. A pink fluffy solid was collected by vacuum filtration andre-dissolved in 4 mL methylene chloride and re-precipitated in methanolto afford a fluffy light solid which was collected by vacuum filtrationand dried in vacuo (65° C., 4 hours) to provide the product polymer XXVI(432 mg). GPC (PS reference) M_(w)=26516 grams per mole, M_(n)=22998grams per mole, PDI=1.15, UV-Vis (chloroform) 275, 296, 308, 331, 348,366, 387, 415.

The structures of product polymers XXV-XXVI discussed in Examples 7-8are gathered in Table 3.

TABLE 3 PRODUCT POLYMERS R³ Entry* Ar¹ L¹ F Q n^(a) m XXV

Br 3.2 2 XXVI

Br 8 2

*Structures are referenced to heterocycle I wherein M = Pd²⁺, “a” = 0,R¹ = R² = H, and R³ = Ar¹(L¹(F)_(n)Q)_(m). ^(a)average value of “n”.Polycyclic and Heterocyclic Olefin Monomers

Example 9

Preparation of 2-bromo-9,9-dioctylfluorene: A mixture of 2-bromofluorene(100 g, 0.4 mol), in DMSO (320 ml), Bu₄NBr (8.0 g, 25 mmol) and NaOH(50%, 160 mL) was degassed with argon for 30 min. To the resultantsolution was added 1-bromooctane (d=1.18 g/mol, 232 mL). The mixture wasstirred under Ar at 60 ° C. for an hour, until HPLC indicated completeconversion of the 2-bromofluorene to product. The reaction mixture wasthen cooled, 600 mL of ether and 400 mL of water were added, and themixture was transferred to a separatory funnel. The aqueous phase wasextracted with ether (2×300 mL), the combined ether layer was washedwith 10% HCl (2×), water (3×) and brine (1×). Removal of solvent invacuo afforded 320 g of an oil. Excess 1-bromooctane (99.12 g) wasremoved by vacuum distillation (120 ° C. for 2 hours, and 150 ° C. for 2hours at 1 torr). The pot residue (˜163.4 g) was shown by ¹H NMR theproduct 2-bromo-9,9-dioctylfluorene (85.3% yield). EI-MS: 470 (M+2), 468(M+). ¹H NMR (CDCl₃) δ 7.4-7.8 (m, 7H), 2.0 (dd, CH₂, 4H), 1.2 (m, CH₂,22H), 0.85 (t, 5H), 0.6 (t, CH₃, 3H). ¹³C NMR (CDCl₃) δ 152.98, 150.32,140.14, 140.03, 129.85, 127.45, 126.90, 126.14, 124.40, 122.88, 121.02,119.73, 55.37, 47.52, 40.28, 31.75, 29.94, 29.19, 23.68, 22.62, 14.17.

Example 10

Preparation of 2-formyl-9,9-dioctylfluorene: To a dry 500 mL flaskequipped with an argon inlet, a rubber septum, and a distillation headwas charged 22.54 g (48.0 mmol) of 9,9-dioctyl-2-bromofluorene and 100mL of toluene. Toluene was then removed by distillation to dry the flaskand starting material. The residue was allowed to cool to roomtemperature and 250 mL of anhydrous ether was added. The resultantsolution was then chilled to −78 ° C. and treated dropwise over 15minutes with 30.6 mL (49.06 mmol) of 1.6M BuLi in hexane. Upon additionof the butyl lithium solution the reaction mixture initially turnedpurple and subsequently turned red. Anhydrous DMF (8 mL) was added andthe resulting mixture was stirred at −78 ° C. for 1 hour and then warmedup to room and stirred for an additional hour. The mixture was quenchedwith 50 mL of 10% HCl and transferred into a separatory funnel. Theorganic phase was washed with 10% HCl (1×), water (2×) and brine (1×),and then dried over MgSO₄. Solvent removal afforded 12 g of crudeproduct. Purification by column chromatography (gradient from 96:4heptanes: EtOAc in heptanes to 90:10 heptanes:EtOAc) afforded 10.2 g of2-formyl-9,9-dimethylfluorene (49.77% yield). EI-MS: 418 (M+), 362,193(100). ¹H NMR (CDCl₃) δ 10.09 (s, 1H), 7.87 (m, 4H), 7.41 (b, 3H), 2.05(m, 4H), 1.30-1.05 (m, 22H), 0.83 (t, 5H), 0.61 (t, 3H). ¹³C NMR (CDCl₃)δ 192.22, 152.11, 151.55, 147.54, 139.53, 135.39, 130.40, 128.78,127.10, 123.09, 120.98, 120.91, 119.93, 70.98, 55.32, 40.24, 31.88,29.92, 29.17, 23.78, 22.59, 14.03.

Exanple 11

Preparation of 2-vinyl-9,9-dioctylfluorene: To a solution ofmethyltriphenylphosphonium bromide (714 mg, 2 mmol) in ether at 0° C.was added dropwise 1.6 M n-BuLi solution in hexane (1.25 mL, 2.00 mmol).The solution was stirred at 0° C. for 40 min and then was warmed to roomtemperature. A solution of 2-formyl-9,9-dioctylfluorene (585 mg, 1.4mmol) was then added and reaction mixture was stirred overnight. Thereaction mixture was quenched with 20 mL of 1% HCl. The mixture wasextracted with ether and the organic layer was washed with NaHCO₃solution, and brine solution, and dried over MgSO₄. The solvent wasremoved in vacuo and the product was purified by column chromatographyon silica gel using hexane as the elutant to afford the purified2-vinyl-9,9-dioctylfluorene (0.2834 g, 49% yield). EI-MS: 416 (M+),360,192 (100). ¹H NMR (CDCl₃) δ 7.66 (m, 2H), 7.42-7.32 (m, 5H), 6.83(dd, 1H), 5.82 (d, 1H), 5.28 (d, 1H), 1.97 (m, 4H), 1.28-1.06 (m, 22H),0.83 (t, 5H), 0.63 (t, 3H). ¹³C NMR (CDCl₃) δ151.09, 151.00, 141.08,140.8, 137.51, 136.47, 127.05, 126.77, 125.21, 122.88, 120.54, 119.69(2C), 112.89, 54.97, 40.39, 31.84, 31.65, 30.09, 29.25, 23.75, 22.65,14.10

Example 12

Preparation of 3,4-dimethylthiophene: A pre-heated 4 L 3-neck roundbottom flask fitted with a reflux condenser and pressure equalizingaddition funnel was purged with nitrogen until cool. The flask was thencharged with 1,3-bis(diphenylphosphino)propane (dppp) NiCl₂ (5.0 grams,mmoles) and suspended in 300 mL dry ether. Then, 3,4-dibromothiophene(200 grams, mmoles) was added via canula. The pressure equalizingaddition funnel was charged with 3.0 M methyl magnesium bromide (800 mL)which was added dropwise over the course of 3 hours. The color of thereaction mixture darkened from bright red initially to a darkorange-brown color. The reaction mixture was heated at reflux for 48hours. Upon cooling, 1.0 liter (L) of 1N hydrochloric acid was added tothe vigorously stirred mixture. The phases were separated and theaqueous phase was extracted with ether (3×500 mL). The organic phase andextracts were combined, washed with brine (1×1.0 L), and dried oversodium sulfate. The volatiles were removed in vacuo leaving a dark brownoil (85 grams). Distillation of the oil at 58° C. at 40 mm Hg yieldedthe product 3,4-dimethylthiophene as a colorless oil (73.2 g). ¹H-NMR(benzene-d₆) δ 6.71 (2H, s), 1.99 (6H, s).

Example 13

Preparation of 2-bromo-3,4-dimethylthiophene: A solution ofN-bromosuccinimide (NBS) (41.85 g, 0.24 mol) in 150 mL of DMF was addeddropwise into a flask containing 3,4-dimethylthiophene (30.0 g, 0.267mol) in dimethylformamide (DMF) (300 mL) at 0° C. over a period of 1 h.After the addition, the cooling bath was removed and the resultingmixture was stirred for 2 h at room temperature. The mixture wasquenched with ice-water (300 mL) and extracted with ether (50 mL) threetimes. The combined organic extracts were washed with water, and driedover MgSO₄. Solvent removal followed by fractional vacuum distillationyielded the product 2-bromo-3,4-dimethylthiophene as a pale yellowliquid (35.0 g, 70%). ¹H NMR (CDCl₃) δ 6.88 (1H, s), 2.20 (3H, s), 2.12(3H, s).

Example 14

Preparation of 2,5-dibromo-3,4-dimethylthiophene: To a solution of3,4-dimethylthiophene (15.0 g, 0.133 mol) in DMF (100 mL) was added asolution of NBS (54 g, 0.85 mol) in DMF (150 mL) dropwise at roomtemperature. After the addition, the reaction mixture was stirred atroom temperature for 2 h. The mixture was poured into ice water andextracted with either (50 mL) three times. The combined organic extractswere washed with water (three times) and dried over MgSO₄. Removal ofthe solvent afforded the product 2,5-dibromo-3,4-dimethylthiophene as ayellow liquid (35 g, 90%). ¹H NMR (CDCl₃) δ 2.14 (6H, s, CH₃).

Example 15

Preparation of 3,4-dimethylthiophene dimer: To a reaction vesselcontaining dry THF (30 mL) was added magnesium turnings (0.60 g, 25mmol) and 2-bromo-3,4-dimethylthiophene (3.5 g, 18.2 mmol) undernitrogen. The resultant mixture was refluxed for 3 h to afford asolution of the Grignard reagent 3,4-dimethylthienylmagnesium bromide.The solution containing the Grignard reagent was transferred to anadditional funnel and added dropwise under nitrogen into a flaskcontaining 2-bromo-3,4-dimethylthiophene (3.5 g, 18.2 mmol) and dpppNiCl₂ (60 mg) in dry THF (30 mL) at room temperature over a period of 30min. Upon completion of the addition, the reaction mixture was heatedovernight at reflux. The mixture was then quenched with a saturatedsolution of ammonium chloride and extracted with ether (3×50 mL). Thecombined organic phases were washed with water and brine, and dried overMgSO₄. Removal solvent and purification by chromatography (silica gel)afforded a crude product which was recrystallized from hexane to give3,4-dimethylthiophene dimer as a white solid (2.41 g, 60%). ¹H NMR(CDCl₃) δ 6.96 (2H, s, aromatic H), 2.22 (6H, s, CH₃), 2.05 (6H, s,CH₃).

Example 16

Preparation of 3,4-dimethylthiophene trimer: The preparation of thetrimer followed a procedure analogous to that used in Example 15. TheGrignard reagent prepared from 2-bromo-3,4-dimethylthiophene (14.3 g, 73mmol) and magnesium turnings (2.4 g, 100 mmol) in dry THF (60 mL) wasadded dropwise under nitrogen into a flask containing2,5-dibromo-3,4-dimethylthiophene (8.0 g, 29.4 mmol) and dppp NiCl₂ (450mg) at room temperature. After the addition, the reaction mixture washeated overnight at reflux. The crude product was isolated as in Example15. Recrystallization from a mixture of hexane and ethanol gave theproduct 3,4-dimethylthiophene trimer as a white solid (7.10 g, 73%). ¹HNMR (CDCl₃) δ 7.01 (2H, s, aromatic H), 2.27 (6H, s, CH₃), 2.16 (12H, s,CH₃).

Example 17

Preparation of 2-formyl-3,4-dimethylthiophene dimer(2-formyl-5-(3′,4′-dimethylthienyl)-3,4-dimethylthiophene):3,4-dimethylthiophene dimer (2.42 g, 11 mmol) was dissolved in 10 mLDMF. A solution of DMF and POCl₃ (30 mL, 4:1 DMF:POCl₃) was addedcautiously at 0° C. and the mixture was stirred overnight at roomtemperature. The reaction mixture was then poured into ice water,neutralized with 25% NaOH solution (to pH˜8). The mixture was thenextracted with dichloromethane. Evaporation of the dichloromethane gavethe crude product which was purified by column chromatography on silicagel. Dichloromethane-petroleum ether (1:3) was used as the eluant. Theproduct 2-formyl-5-(3′,4′-dimethylthienyl)-3,4-dimethylthiophene (2.3 g,85% yield) was characterized by NMR. 1H NMR (CDCl3) δ 10.07 (1H, s,CHO), 7.03 (1H, s, aromatic H), 2.53 (3H, s, CH3), 2.22 (3H, s, CH3),2.10 (3H, s, CH3), 2.08 (3H, s, CH3).

Example 18

Preparation of 2-formyl-3,4-dimethylthiophene trimer (Method A): Asolution of 1.5 M n-butyllithium (3.4 mL, 5.1 mmol) in ether was addeddropwise under argon to a solution of 3,4-dimethylthiophene trimer (1.62g, 4.8 mmol, See Example 16) in dry THF (10 mL) at −70° C. and theresultant solution was warmed to −50° C. Next, 0.4 mL (5.4 mmol) of DMFwas added dropwise and the mixture allowed to warm to room temperatureovernight. The mixture was poured into a mixture of 1 liter of 12 M HCland crushed in certain embodiments and thereafter extracted with ether.The organic layers were combined, washed with water, and dried overMgSO₄. After evaporation of the solvent, the residue was purified bycolumn chromatography (silica gel, hexane/CH₂Cl₂ (v:v) 3:1) to give theproduct 2-formyl-3,4-dimethylthiophene as a yellow solid (0.98 g, 56%)and recovered unreacted trimer (0.55 g). ¹H NMR (CDCl₃) δ 10.08 (1H, s,CHO), 6.99 (1H, s, aromatic H), 2.53 (3H, s, CH₃), 2.22 (3H, s, CH₃),2.16 (3H, s, CH₃), 2.13 (3H, s, CH₃), 2.10 (6H, s CH₃).

Example 19

Preparation of 2-formyl-3,4-dimethylthiophene trimer (Method B): To asolution of 3,4-dimethylthiophene trimer (3.7 g, 11 mmol) in 20 mL of aDMF: CHCl₃ (1:1, v:v) solvent mixture, was added 20 mL of a solution ofDMF and POCl₃ (4:1, v:v). The DMF:POCl₃ mixture was added cautiously,dropwise at 0° C. Following the addition, the reaction mixture wasallowed to warm to ambient temperature and was stirred overnight. Thereaction mixture was then poured into ice water and neutralized with 25%NaOH solution to pH˜8. The aqueous mixture was extracted withdichloromethane. Upon solvent removal the residue was subjected topurification by column chromatography using silica gel and adichloromethane-petroleum ether (1:3) mixed solvent as the elutingsolution to yield pure product 2-formyl-3,4-dimethylthiophen trimer 2.2g (Yield: 55%) ¹H NMR (CDCl3) δ 10.09 (1H, s, CHO), 7.00 (1H, s,aromatic H), 2.54 (3H, s, CH3), 2.23 (3H, s, CH3), 2.16 (3H, s, CH3),2.13 (3H, s, CH3), 2.11 (6H, s, CH3), and the corresponding trimerdialdehyde 1.57 g (Yield: 37%) ¹H NMR (CDCl3) δ 10.09 (2H, s, CHO), 2.54(6H, s, CH3), 2.15 (12H, m, CH3).

Example 20

Preparation of 2-vinyl-3,4-dimethylthiophene trimer: To a solution ofmethyltriphenylphosphonium bromide (714 mg, 2 mmol) in ether at 0° C.was added dropwise 1.6 M n-BuLi solution in hexane (1.25 mL, 2.00 mmol).The resultant solution was stirred at 0° C. for 40 min and then waswarmed to room temperature. A solution of 2-formyl-3,4-dimethylthiophenetrimer (432 mg, 1.2 mol) was added slowly and the mixture was stirredovernight. The reaction mixture was quenched with ammonium chloridesolution and diluted with ether. The organic phase was washed with waterand brine, and dried with MgSO₄. The ether was removed in vacuo toafford the crude product as an oil (260 mg). Column chromatography (2%EtOAc in hexane) afforded the purified 2-vinyl-3,4-dimethylthiophenetrimer (140 mg, 37% yield). EI-MS: 358 (M+). ¹H NMR (CDCl₃) δ 6.98 (s,1H), 6.90 (dd, 1H), 5.52 (d, 1H), 1.15 (d, 1H), 2.22 (s, 1H), 2.19 (s,1H), 2.11 (s, 1H), 2.10 (s, 1H), 2.09 (s, 1H), 2.08 (s, 1H).

Example 21

Preparation of 2-bromo-3-methyl-4-cyclohexylthiophene: To anicebath-chilled solution of 3-methyl-4-cyclohexylthiophene (10 g, 55.55mmol) in DMF (60 mL) was added solid N-bromosuccinimide (9.89 g, 55.55mmol). After addition, the mixture was allowed to warm to roomtemperature and was stirred for about 1 hr at which point HPLC analysisindicated the reaction was complete. The product mixture was poured into200 mL of cold water and the aqueous phase was extracted with ether(3×125 mL). The combined ether extracts were washed with water (3×250mL) and brine (1×200 mL), then passed through a cone of DRIERITE.Solvent was removed by rotary evaporation to afford the crude product2-bromo-3-methyl-4-cyclohexylthiophene (13.6 g, 94%) as a light amberoil which was judged to be of greater than 95% purity product. ¹H NMR(CDCl₃) δ 6.88 (s, 1, ArH), 2.53 (m, 1, cyclohexylmethine) 2.19 (s,3,ArCH₃), 1.9 and 1.35 ppm (m, 10, cyclohexyls).¹³C NMR 147.81, 135.93,118.32, 109.44 (thiophene carbons), 39.27, 33.55, 26.86, 26.24 and 13.73(aliphatic carbons). 2D NMR confirmed that the bromine was bonded to thecarbon adjacent to the 3-methyl substituent.

Example 22

Preparation of 2-formyl-3-methyl-4-cyclohexylthiophene: To a solution of3-methyl-4-cyclohexylthiophene (3 g, 17 mmol) in DMF (10 mL) was added10 mL of a solution prepared from DMF and POCl₃ (4:1, v:v). Thetemperature was maintained at about 0° C. during the addition. Thereaction mixture was then stirred overnight at room temperature, andpoured into ice water. After neutralization with 25% NaOH solution topH˜8, the product was extracted with dichloromethane. The solvent wasevaporated to afford the crude product2-formyl-3-methyl-4-cyclohexylthiophene as a solid which was purified bycolumn chromatography (dichloromethane-petroleum ether (1:3)) (2.85 g,yield: 83%). ¹H NMR (CDCl₃) δ 10.07 (s, 1, CHO), 7.28 (s, 1, thienyl-H),2.58 (m,1,cyclohexyl methane), 2.53 (s, 3,CH₃),1.89 and 1.37 m, 10,cyclohexyl).

Example 23

Preparation of 5-bromo-3-methyl-4-cyclohexyl-2-formylthiophene: To asolution of 2-formyl-3-methyl-4-cyclohexylthiophene (4.1 g, 20 mmol, SeeExample 22) in 30 mL of a mixture prepared from acetic acid andchloroform (1:1), was added solid N-bromosuccinimide (5.3 g, 30 mmol)slowly in portions at 0° C. The reaction mixture was then stirredovernight at room temperature, poured into water, and extractedrepeatedly with dichloromethane. The combined organic layers were washedwith saturated NaHCO₃ and brine solutions, and dried over anhydrousNa₂SO₄. After the solvent was removed by rotary evaporation, theremaining solid was purified by column chromatography using silica geland a dichloromethane-petroleum ether (2:3) as eluant. The solvent wasremoved by rotary evaporation yielding 3.3 g white solid (57%). ¹H NMR(CDCl₃) δ 9.97 (s, 1, CHO), 2.88 (m, 1,cyclohexyl methane), 2.59 (s,3,CH₃), 1.87 and 1.34 m, 10, cyclohexyl)

Example 24

Preparation of 3-methyl-4-cyclohexylthiophene-2-boryl pinacolate:2-bromo-3-methyl-4-cyclohexylthiophene (5 g, 19.2 mmol) was dissolved in30 ml of anhydrous THF. Magnesium turnings (0.55 g, 23 mmol) were addedand then the mixture was refluxed for 4 hours to form the correspondingGrignard reagent. A solution of isopropoxypinacolato borane (5.0 g, 26.9mmole) was added dropwise to the Grignard reagent at −78° C. The mixturewas stirred overnight, and then saturated NH₄Cl solution (100 mL) wasadded. The organic layer was separated, dried over anhydrous Na₂SO₄, andthe solvent was removed in vacuo. The reside was subjected to columnchromatography to afford the purified product3-methyl-4-cyclohexylthiophene-2-boryl pinacolate (3.0 g, 51%) as awhite solid. ¹H NMR (CDCl₃) δ 7.20 (s, 1H thienyl-H), 2.54 (m, 1H,cyclohexyl methine), 2.42 (s, 3H, CH₃), 1.88 and 1.34 (m, 10H,cyclohexyl) and 1.35 ppm (s, 12H, pinacol methyls).

Example 25

Preparation of 2-formyl-3-methyl4-cyclohexylthiophene dimer:5-bromo-3-methyl-4-cyclohexyl-2-formylthiophene (1.5 g, 5.2 mmol),3-methyl-4-cyclohexylthiophene-2-boryl pinacolate (1.9 g, 6.24 mmol) andBu₄NBr (33 mg, 0.1 mmol) were added to a 100 ml flask. The mixture ofsolids was evacuated for 2 hours, then dissolved in dry toluene (30 ml)under argon with stirring. Tetrakis(triphenylphosphine)palladium (100mg, 0.09 mmol) was added and the solution was heated to 95° for 16hours. Afterwards, an additional aliquot of boronate (0.5 g) andtetrakis(triphenylphosphine)palladium (50 mg) were added. The reactionwas checked, after stirring an additional 20 hours, and found to becomplete. The mixture was poured into a saturated solution of ammoniumchloride, and extracted with toluene (3×20 mL). The combined organiclayers were washed with brine and dried over anhydrous Na₂SO₄. After thesolvent was removed by rotary evaporation. The remaining oil waspurified by column chromatography (CH₂Cl_(2:)petroleum ether, 2:3) toafford the product 2-formyl-3-methyl-4-cyclohexylthiophene dimer as ayellow solid (1.5 g, 75%). ¹H NMR (CDCl₃) δ 10.08 (s, 1, CHO), 7.01 (s,1,thienyl-H), 2.67 (m,1,cyclohexyl methane), 2.65 (s, 3,CH₃), 2.52(m,1,cyclohexyl methane), 2.07 (s, 3,CH₃), 1.78 and 1.31 (m, 20,cyclohexyl). ¹³C NMR (CDCl₃) δ 182.5, 148.3, 147.9, 146.5, 140.4, 138.2,136.7, 128.6, 119.4, 39.7, 38.8, 33.8, 31.3, 27.1, 26.9, 26.3, 25.9,14.01, 13.3.

Example 26

Preparation of 2-vinyl-3-methyl-4-cyclohexylthiophene dimer: To asolution of methyltriphenylphosphonium bromide (4.983 g, 13.96 mmol) inether at 0° C. was added dropwise 1.6 M n-BuLi solution in hexane (8.7ml, 13.96 mmol). The solution was stirred at 0° C. for 40 min and thenwas warmed to room temperature. A solution of2-formyl-3-methyl-4-cyclohexylthiophene dimer (2.7 g, 6.98 mmol) in aminimum of ether was added. The solution was stirred overnight. Thereaction mixture was then diluted with ether and washed with water andbrine, and dried over MgSO₄. The solvent was removed in vacuo and thecrude product was purified by column chromatography using hexane as theeluant to afford 2-vinyl-3-methyl-4-cyclohexylthiophene dimer 1.32 g(50% yield) as a white solid. ¹H NMR (CDCl₃) δ 6.98 (s, 1H), 6.90 (dd,1H), 5.52 (d, 1H), 1.15 (d, 1H), 2.22 (s, 1H), 2.19 (s, 1H), 2.11 (s,1H), 2.10 (s, 1H), 2.09 (s, 1H), 2.08 (s, 1H). ¹³C NMR (CDCl₃) δ 147.93,146.37, 137.41, 136.09, 134.78, 129.97, 128.44, 127.57, 118.61, 112.7,40.07, 38.86, 33.74, 31.37, 27.19, 26.91, 26.30, 26.12, 13.61, 13.33.

The structures of thiophene derivatives discussed in Examples 12-26 aregathered in Table 4.

TABLE 4 THIOPHENE DERIVATIVES Example No. Chemical Name Structure 123,4-dimethylthiophene

13 2-bromo-3,4- dimethylthiophene

14 2,5-dibromo-3,4- dimethylthiophene

15 3,4-dimethylthiophene dimer

16 3,4-dimethylthiophene trimer

17 2-formyl-3,4- dimethylthiophene dimer

18/19 2-formyl-3,4- dimethylthiophene trimer

20 2-vinyl-3,4- dimethylthiophene trimer

21 2-bromo-3-methyl-4- cyclohexylthiophene

22 2-formyl-3-methyl-4- cyclohexylthiophene

23 5-bromo-3-methyl-4- cyclohexyl-2- formylthiophene

24 3-methyl-4- cyclohexylthiophene-2- boryl pinacolate

25 2-formyl-3-methyl-4- cyclohexylthiophene dimer

26 2-vinyl-3-methyl-4- cyclohexylthiophene dimer

The foregoing examples are merely illustrative, serving to illustrateonly some of the features of the invention. The appended claims areintended to claim the invention as broadly as it has been conceived andthe examples herein presented are illustrative of selected embodimentsfrom a manifold of all possible embodiments. Accordingly, it isApplicants' intention that the appended claims are not to be limited bythe choice of examples utilized to illustrate features of the presentinvention. As used in the claims, the word “comprises” and itsgrammatical variants logically also subtend and include phrases ofvarying and differing extent such as for example, but not limitedthereto, “consisting essentially of” and “consisting of.” Wherenecessary, ranges have been supplied, those ranges are inclusive of allsub-ranges there between. It is to be expected that variations in theseranges will suggest themselves to a practitioner having ordinary skillin the art and where not already dedicated to the public, thosevariations should where possible be construed to be covered by theappended claims. It is also anticipated that advances in science andtechnology will make equivalents and substitutions possible that are notnow contemplated by reason of the imprecision of language and thesevariations should also be construed where possible to be covered by theappended claims.

1. A composition comprising heterocyclic structure I

wherein M is a divalent, trivalent or tetravalent metal ion; “a” is 0,1, 2, or a non-zero fraction having a value between 0 and 1; Y isindependently at each occurrence a charge balancing counterion; R¹ andR² are independently at each occurrence a hydrogen, a halogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, a C₂-C₂₀ aromaticradical, or R¹ and R² may together form a divalent aliphatic radical, adivalent cycloaliphatic radical, or a divalent aromatic radical; R³ isindependently at each occurrence an organic radical having structure II

wherein Ar¹ is a C₂-C₅₀ aromatic radical; L¹ is a C₁-C₂-aliphaticradical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; Fis independently at each occurrence a structural unit derived from anolefin monomer of formula III,

R⁴ and R⁵ are independently hydrogen, C₁-C₂₀ aliphatic radical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; L² is a bond, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical; and R⁶ is hydrogen, halogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;“n” is independently at each occurrence an integer from 1 to 200; Q isindependently at each occurrence a hydrogen, a halogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical; and “m” is independently at each occurrence an integer from 1to
 10. 2. The composition according to claim 1, wherein “a” is 0, and Mis selected from the group consisting of Pd²⁺ and Pt²⁺.
 3. Thecomposition according to claim 1, wherein “a” is 0, and M is Pt²⁺. 4.The composition according to claim 1, wherein “a” is 0, and M is Pd²⁺.5. The composition according to claim 1, wherein “a” is 0; M is selectedfrom the group consisting of Pd²⁺ and Pt²⁺; R¹ and R² are H; Ar¹ is anaromatic radical of formula XII;

L¹ is a divalent aliphatic radical having structure XIII;

F is a moiety having structure XIV

wherein R⁴ and R⁵ are independently at each occurrence hydrogen, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical, and R⁶ is independently at each occurrence a hydrogen,a halogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical,or a C₂-C₂₀ aromatic radical; “n” is independently at each occurrence aninteger from 2 to 10; Q is Br; and “m” is 1 or
 2. 6. The compositionaccording to claim 1, wherein “a” is 0; M is selected from the groupconsisting of Pd²⁺ and Pt²⁺; R¹ and R² are H; Ar¹ is an aromatic radicalselected from the group consisting of divalent aromatic radicals XI andXII;

L¹ is a divalent aliphatic radical having structure XIII;

F is a moiety having structure XV

wherein R⁴ is independently at each occurrence hydrogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical; L² is a bond, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; and R⁶ isindependently at each occurrence a halogen, a C₁-C₂₀ aliphatic radical,a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; “b” isindependently at each occurrence 0, 1, or 2; “c” is a number from 0 to10; “n” is independently at each occurrence an integer from 2 to 10; Qis Br; and “m” is 1 or
 2. 7. The composition according to claim 1, saidcomposition having a number average molecular weight in a range from1000 grams per mole to 500,000 grams per mole.
 8. The compositionaccording to claim 1, said composition having a number average molecularweight in a range from 1000 grams per mole to 25,000 grams per mole. 9.The composition according to claim 1, said composition having a numberaverage molecular weight in a range from 2000 grams per mole to 10,000grams per mole.
 10. The composition according to claim 1, wherein thegroup Q is a C₉ cycloaliphatic radical having structure XVI


11. An organic phosphor comprising heterocyclic structure I

wherein M is a divalent, trivalent or tetravalent metal ion; “a” is 0,1, 2, or a non-zero fraction having a value between 0 and 1; Y isindependently at each occurrence a charge balancing counterion; R1 andR2 are independently at each occurrence a hydrogen, a halogen, a C1-C20aliphatic radical, a C3-C20 cycloaliphatic radical, a C2-C20 aromaticradical, or R1 and R2 may together form a divalent aliphatic radical, adivalent cycloaliphatic radical, or a divalent aromatic radical; R3 isindependently at each occurrence an organic radical having structure II

wherein Ar1 is a C2-C50 aromatic radical; L1is a C1-C20 aliphaticradical, a C3-C20 cycloaliphatic radical, or a C2-C20 aromatic radical;F is independently at each occurrence a structural unit derived from anolefin monomer of formula III,

R⁴ and R⁵ are independently hydrogen, C₁-C₂₀ aliphatic radical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; L² is a bond, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical; and R⁶ is hydrogen, halogen, a C₁-C₂₀ aliphaticradical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromatic radical;“n” is independently at each occurrence an integer from 1 to 200; Q isindependently at each occurrence a hydrogen, a halogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical; and “m” is independently at each occurrence an integer from 1to
 10. 12. The organic phosphor according to claim 11, wherein “a” is 0,and M is selected from the group consisting of Pd²⁺ and Pt²⁺.
 13. Theorganic phosphor according to claim 11, wherein “a” is 0, and M is Pt²⁺.14. The organic phosphor according to claim 11, wherein “a” is 0, and Mis Pd²⁺.
 15. The organic phosphor according to claim 11, wherein “a” is0; M is selected from the group consisting of Pd²⁺ and Pt²⁺; R¹ and R²are H; Ar¹ is an aromatic radical of formula XII;

L¹ is a divalent aliphatic radical having structure XIII;

F is a moiety having structure XIV

wherein R⁴ and R⁵ are independently at each occurrence hydrogen, aC₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀aromatic radical, and R⁶ is independently at each occurrence a hydrogen,a halogen, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical,or a C₂-C₂₀ aromatic radical; “n” is independently at each occurrence aninteger from 2 to 10; Q is Br; and “m” is 1 or
 2. 16. The organicphosphor according to claim 11, wherein “a” is 0; M is selected from thegroup consisting of Pd²⁺ and Pt²⁺; R¹ and R² are H; Ar¹ is an aromaticradical selected from the group consisting of divalent aromatic radicalsXI and XII;

L¹ is a divalent aliphatic radical having structure XIII;

F is a moiety having structure XV

wherein R⁴ is independently at each occurrence hydrogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical, and R⁶ is independently at each occurrence a halogen, a C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₂-C₂₀ aromaticradical; L² is a bond, a C₁-C₂₀ aliphatic radical, a C₃-C₂₀cycloaliphatic radical, or a C₂-C₂₀ aromatic radical; “b” isindependently at each occurrence 0, 1, or 2; “c” is a number from 0 to10; “n” is independently at each occurrence an integer from 2 to 10; Qis Br; and “m” is 1 or
 2. 17. The organic phosphor according to claim11, said composition having a number average molecular weight in a rangefrom 1000 grams per mole to 500,000 grams per mole.
 18. The organicphosphor according to claim 11, said composition having a number averagemolecular weight in a range from 2000 grams per mole to 10,000 grams permole.
 19. The organic phosphor according to claim 11, wherein the groupQ is a C₉ cycloaliphatic radical having structure XVI


20. The organic phosphor according to claim 11, wherein the phosphor ischaracterized by a red phosphorescence.